HK1194417B - Low molecular weight products and use thereof as reversible or permanent lowtemperature crosslinking agent in diels-alder reactions - Google Patents

Description

Low molecular weight products and their use as reversible or permanent low temperature crosslinkers in diels-alder reactions

Technical Field

The present invention relates to low molecular weight products, their preparation and use as reversible or permanent crosslinkers in polymers or polymer networks, wherein the linking or crosslinking of the resulting polymers is caused via a diels-alder reaction.

Background

The process of reversible crosslinking of polymers is of great interest for a wide range of applications. For example, in adhesive applications, a multiplicity of possibilities for the automotive industry or the semiconductor industry are described. However, such adhesives are also of interest in the construction of machines, precision machinery, or in the construction industry.

In addition to adhesive applications, polymers capable of reversible crosslinking may also be of interest in sealants, in coatings such as varnishes or paints, or in the production of molded articles, for example via rapid prototyping processes.

As for DierThe best known crosslinker molecules of the S-Alder crosslinking reaction are said to be known here as bismaleimide building blocks which have been commercially available since a long time (from Evonik AG)）。

For some years, mainly in academia, methods of constructing block copolymers have been studied under the upper term "Click chemistry". Here, two different homopolymers with a linkable end group are combined with one another and are linked to one another, for example by a diels-alder reaction, a diels-alder-like reaction or another cycloaddition. The purpose of this reaction is to build thermally stable, linear and possibly high molecular weight polymer chains. For example, Inglis et al (Macromolecules 2010,43, pages 33 to 36) describe for this purpose polymers having cyclopentadienyl end groups, which are obtainable from polymers prepared by means of ATRP. These cyclopentadienyl groups are capable of reacting very rapidly with polymers bearing electron-deficient dithioesters as end groups in heterodiels-alder reactions (Inglis et al, angelw.chem.int.ed.2009, 48, p 2411-.

The use of monofunctional RAFT polymers for attachment to monofunctional polymers bearing dihydrothiopyran groups via heterodiels-alder reactions is described in Sinnwell et al (chem. AB diblock copolymers can be achieved in this way. This rapid modification of heterodiels-alder linkages for the synthesis of AB block copolymers having dithioester groups present after RAFT polymerization and having dienyl end groups is described in Inglis et al (angelw. chem. int.ed.2009,48, pages 2411-14) and Inglis et al (macromol. rapdcommun.2009,30, pages 1792-98). Similar preparation of multi-arm star polymers is found in Sinnwell et al (J.pol.Sci.: Part A: pol.Chem.2009,47, pages 2207-13).

US6,933,361 describes a system for producing easily repairable transparent mouldings. The system consists of two multifunctional monomers that polymerize via diels-alder reactions to form a highly dense network. Here, one of the functional groups is maleimide and the other functional group is furan. This thermal conversion of the highly dense network is used for its repair. Crosslinking takes place at temperatures above 100 ℃. Partial reverse reactions occur at even higher temperatures.

In Syrett et al (Polymer. chem.2010, DOI: 10.1039/b9py00316 a), star polymers are described for use as flow improvers in oil. These polymers have self-healing properties that can be controlled using reversible diels-alder reactions. For this purpose, monofunctional polymethacrylate arms are combined with polymethacrylates which have, in the middle of the chain, as fragments of the initiator used, groups which are available for reversible diels-alder reactions.

Patent application DE102010001987.9 discloses crosslinkable systems having a thermoreversible crosslinking mechanism based on Diels-Alder or heteroDiels-Alder reactions. DE102010001992.5 discloses similar systems with controllable viscosity using the same thermoreversible mechanism.

US4,513,125A discloses compositions for special cathodic electrophoretic paint coatings in which a polydiene-functionalized epoxy-amine and a polydiene-functionalized polyisocyanate oligomer are reacted with each other at elevated temperatures. The polydienophile-functionalized polyisocyanate oligomer has a functionality of at least 3. Particular mention may be made of furfuryl alcohol and/or furfuryl amine, 2-hydroxymethyl-1, 3-butadiene, 2-aminomethyl-1, 3-butadiene or mixtures thereof. However, sorbitol derivatives are not mentioned.

Disclosure of Invention

Purpose(s) to

The object of the present invention was to find low molecular weight crosslinker molecules for diels-alder reactions at preferably low temperatures, which are easy to synthesize and can be used in a wide variety of ways and have the possibility of retro diels-alder reactions for reversible crosslinking, which molecules are additionally also particularly ecological.

This object is achieved by the novel reaction products of the present invention.

The present invention provides a reaction product of:

A) at least one isocyanate and/or amine of the formula 1 having at least two functional groups per molecule,

it has the following definitions:

n=0、1，

X=NCO、NH₂、NHA，

a = H, is simultaneously or independently of one another an alkyl radical having 1-16 carbon atoms, a cyclic hydrocarbon radical, an aromatic hydrocarbon radical, where this radical may also contain heteroatoms and/or functional groups and/or double bonds,

r = aliphatic or cycloaliphatic hydrocarbon radicals, which may also contain heteroatoms and/or functional groups and/or double bonds,

and

B) at least one diene of formula 2 having functional groups

It has the following definitions:

Y=CH₂OH、COOH、COOA、CH₂NH₂、CH₂NHA，

A. z and R¹-R⁴= alkyl, cyclic hydrocarbon, aromatic hydrocarbon radicals containing 1 to 16 carbon atoms simultaneously or independently of one another, where these radicals may also containHeteroatoms and/or functional groups and/or double bonds,

wherein all functional groups X of A) have been reacted with an equivalent amount of B).

It has surprisingly been found that the compounds according to the invention can already be crosslinked with dienophiles even at room temperature or at only slightly elevated temperatures and that this crosslinking can be reversed again at higher temperatures by at least 50%.

It has been found that these systems crosslink very rapidly even at room temperature, optionally with the addition of a crosslinking catalyst. It has also been found that these networks can be restored to thermoplastic materials simply and almost completely again, even at very low temperatures, for example slightly above 80 ℃. It has also been found, very surprisingly, that renewed crosslinking can then take place again without further addition of crosslinking agent and/or catalyst, for example via pure cooling. Furthermore, it is of particular effect that these cycles consisting of crosslinking and conversion back to thermoplastic material can be carried out at least three times, preferably at least five times, without any major loss of properties of the network.

Suitable isocyanate components A) are aliphatic, cycloaliphatic and araliphatic diisocyanates (i.e.aryl-substituted aliphatic diisocyanates), such as are described, for example, in Houben-Weyl, Methoden der organischen Chemie (methods of organic chemistry), Vol. 14/2, pp. 61-70, and W.Siefken, Justus Liebigs Ananalen der Chemie562,75-136, such as 1, 2-ethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2, 4-trimethyl-1, 6-hexamethylene diisocyanate (TMDI), 2,4, 4-trimethyl-1, 6-hexamethylene diisocyanate (TMDI) and mixtures thereof, 1, 9-diisocyanato-5-methylnonane, 1, 8-diisocyanato-2, 4-dimethyloctane, 1, 12-dodecane diisocyanate, ω' -diisocyanatodipropyl ether, cyclobutene-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, 3-isocyanatomethyl-3,5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1, 4-diisocyanatomethyl-2, 3,5, 6-tetramethylcyclohexane, decahydro-8-methyl-1, 4-methano-naphthalene-2, 5-yl-dimethylene diisocyanate, decahydro-8-methyl-1, 4-methano-naphthalene-3, 5-yl-dimethylene diisocyanate, hexahydro-4, 7-methyleneindan-1, 5-yl-dimethylene diisocyanate, hexahydro-4, 7-methyleneindan-2, 5-yl-dimethylene diisocyanate, hexahydro-4, 7-methyleneindan-1, 6-yl-dimethylene diisocyanate, hexamethylene-4, 7-methyleneindan-1, 6-yl-dimethylene diisocyanate, Hexahydro-4, 7-methyleneindan-2, 5-yldimethylene diisocyanate, hexahydro-4, 7-methyleneindan-1, 5-yldiisocyanate, hexahydro-4, 7-methyleneindan-2, 5-yldiisocyanate, hexahydro-4, 7-methyleneindan-1, 6-yldiisocyanate, hexahydro-4, 7-methyleneindan-2, 6-yldiisocyanate, 2, 4-hexahydrotolylene diisocyanate, 2, 6-hexahydrotolylene diisocyanate, 4 '-methylenedicyclohexyl diisocyanate (4, 4' -H `)₁₂MDI), 2 '-methylenedicyclohexyl diisocyanate (2, 2' -H)₁₂MDI), 2, 4-methylenedicyclohexyl diisocyanate (2, 4-H)₁₂MDI) or any mixture of these isomers, 4 '-diisocyanato-3, 3',5,5 '-tetramethyldicyclohexylmethane, 4' -diisocyanato-2, 2',3,3',5,5',6,6' -octamethyldicyclohexylmethane, omega, omega' -diisocyanato-1, 4-diethylbenzene, 1, 4-diisocyanatomethyl-2, 3,5, 6-tetramethylbenzene, 2-methyl-1, 5-diisocyanatopentane (MPDI), 2-ethyl-1, 4-diisocyanatobutane, 1, 10-diisocyanatodecane, 1, 5-diisocyanatohexane, 1, 3-diisocyanatomethylcyclohexane, 1, 4-diisocyanatomethylcyclohexane and any mixtures of these compounds. Other suitable isocyanates are described in the articles given on page 122 and subsequent pages of Annalen. 2, 5-bis (isocyanatomethyl) bicyclo [2.2.1]Heptane (NBDI) and/or (2, 6) -bis (isocyanatomethyl) bicyclo [2.2.1]Heptane (NBDI), either neat or as a mixed component, is also suitable. These diisocyanates are nowadays usually prepared by the phosgene route or by the urea process. The products of both processes are equally suitable for use in the process of the invention.

Aliphatic and cycloaliphatic diisocyanates are particularly preferably used. Very particular preference is given to using IPDI, TMDI, HDI and/or H₁₂MDI, alone or in a mixture.

Another preferred class of polyisocyanates as component A) are compounds having more than two isocyanate groups per molecule which are prepared by dimerizing, trimerizing, allophanatizing, biuretizing and/or urethanizing simple diisocyanates, examples being such simple diisocyanates, for example IPDI, TMDI, HDI and/or H₁₂MDI, a reaction product with a polyol (e.g. glycerol, trimethylolpropane, pentaerythritol) and/or a multifunctional polyamine.

Particular preference is also given to using isocyanurates which can be obtained by trimerizing simple diisocyanates. Very particular preference is given to using IPDI, HDI and/or H₁₂The trimers of MDI, individually or in mixtures.

Also suitable as component A) are aliphatic, cycloaliphatic and araliphatic (i.e.aryl-substituted aliphatic) amines having at least two amino groups in the molecule.

Particularly preferred are diamines selected from the group consisting of: 1, 3-and 1, 4-diaminomethylcyclohexane, hexane-1, 6-diamine (HDA), 2, 4-and/or 2,4, 4-trimethylhexane-1, 6-amine and mixtures thereof, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (isophoronediamine, IPDA), 4,4 '-methylenedicyclohexyldiamine, 2, 4-methylenedicyclohexyldiamine, 2' -methylenedicyclohexyldiamine and also the isomers thereof (H₁₂MDA), polyetherdiamines. Mixtures of the amines may also be used.

Particularly preferred are IPDA, HDA and/or H₁₂MDA。

As diene B), use is made of a diene of the formula 2 having only one functional group

It has the following definitions:

Y=CH₂OH、COOH、COOA、CH₂NH₂、CH₂NHA,

wherein

A. Z and R¹-R⁴Simultaneously or independently of one another, are alkyl groups having 1 to 16 carbon atoms, cyclic hydrocarbon groups, aromatic hydrocarbon groups, where these groups may also contain heteroatoms and/or functional groups and/or double bonds.

The radical Z is here an inert radical which does not react with component A).

The group Y is reacted with the functional group X of component A) to give a reaction product.

Particular preference is given to using sorbitol 3 and/or sorbic acid 4.

Another preferred class of dienes B) are the so-called retinoids of the following general formula 5:

vitamin A and derivatives

F=OH、COOH、COOK、CHO，

Wherein K is an alkyl radical having 1 to 6 carbon atoms, a cyclic hydrocarbon radical, an aromatic hydrocarbon radical, where this radical may also contain heteroatoms and/or functional groups and/or double bonds,

preferably of formula 6:

vitamin A

It will be appreciated by the person skilled in the art that the functional groups of compounds A) and B) must be selected such that they react with one another.

Mention may be made here, as examples of reaction products according to the invention, of the reaction of sorbitol with isophorone diisocyanate to obtain difunctional diene building blocks capable of undergoing a diels-alder reaction:

as examples of reaction products with trimers (isocyanurates) according to the invention, mention may be made here of the reaction of sorbitol with isophorone isocyanurate to give trifunctional diene building blocks capable of diels-alder reactions:

dienes can be made from sorbitol, which is a renewable raw material. It is a derivative of sorbose, which is particularly ecological. The same is true of retinoids.

The invention further provides for the use of the compounds according to the invention for reversibly or permanently crosslinking with compounds containing at least one reactive double bond (also referred to below as dienophiles).

Dienophiles are defined as compounds having a reactive double bond which can react with the two double bonds of the reaction product of the invention by means of a diels-alder reaction. This reaction also proceeds in the reverse direction, with the individual components being formed again: thus, the reaction is reversible and is called retro Diels-Alder reaction. In this case, formulations composed of at least two different components are crosslinked at room temperature using a Diels-Alder reaction or a heteroDiels-Alder reaction. In a second method step, at least 50%, preferably at least 90%, more preferably at least 99% of the crosslinking sites are detached again by means of a retro diels-alder reaction or a retro hetero diels-alder reaction at a higher temperature.

In a preferred embodiment, the dienophile component is a difunctional polymer prepared using Atom Transfer Radical Polymerization (ATRP). In this case, the functionalization process with diene groups takes place by means of substitution reactions of the polymer-analogous transition of the terminal halogen atom or by substitution reactions which take place during the termination process. This substitution reaction can be carried out, for example, by adding a thiol functionalized with diene groups.

The dienophile is preferably a compound containing a carbon-sulfur double bond, and therefore, the preferred crosslinking reaction is a heterodiels-alder reaction.

In the same preferred embodiment, the dienophile component used may be a low molecular weight organic compound containing 3 to 4 dithioester groups, which, according to the above detailed description, has a group Z which greatly reduces the electron density of the C = S double bond.

Particularly preferred dienophiles are dithioesters.

Very particularly preferred dienophiles are compounds having the following structure

Wherein Z is an electron withdrawing group, preferably a strongly electron withdrawing group, R^mAre polyvalent organic radicals, preferably polyfunctional alcohols, polyfunctional halogenated compounds, polyfunctional carboxylic acids or polyfunctional amines based on branched or linear alkyl groups, aromatic groups or combinations of alkyl and aromatic groups. Or, R^mBut may also be a polymer. The number n of dithioester groups being 2A number of from 20, preferably from 2 to 10, more preferably from 2 to 4.

In a preferred embodiment, the group Z is a 2-pyridyl, phosphoryl or sulfonyl group. Also contemplated are cyano or trifluoromethyl groups, in addition to any other group Z which very strongly reduces the electron density of the C = S double bond and thus allows a fast diels-alder reaction.

Polymers which can be crosslinked reversibly or permanently, which can be obtained simply by means of the crosslinker molecules of the invention, are of great interest for a wide range of applications. As examples of releasable adhesive applications, numerous possibilities for the automotive industry or the semiconductor industry are described, which are well known to the person skilled in the art. However, such adhesives are also of interest in the construction of machines, precision mechanical equipment, or in the construction industry. The formulations or methods of the present invention can be used in a wide variety of applications. The following list shows some preferred fields of application by way of example, without restricting the invention in any way in this respect. Examples of such preferred fields of application are adhesives, molding compounds, inks, sealants, coatings such as varnishes or paints, composites, or for the production of moldings, for example via rapid prototyping processes.

An example of the use of the crosslinkable and decrosslinkable materials described herein in the field of rapid prototyping can be found in the FDM (fused deposition modeling) field or in 3D printing by inkjet methods using low viscosity melts.

The invention and its applicability are described in more detail by the following examples.

Detailed Description

Examples

Preparation of sorbitol-IPDI adduct or sorbitol-T1890 adduct is described

Example 1

IPDI-sorbitol adduct (IPDI = isophorone diisocyanate) 2

In a 500ml three-necked flask, sorbitol was melted (60 ℃) and DBTL (dibutyltin dilaurate), Jonol CP and acetone were added beforehand. The mixture was then heated to 40 ℃. IPDI was subsequently added dropwise at 40 ℃ over 3 hours. The reaction mixture contained no NCO after 6 hours at 40 =0.67 wt%; stirring was continued for a further 6 hours at 40 ℃ with NCO content =0.12 wt%. Thereafter, the acetone was removed in a vacuum drying oven at 40 ℃ and the solid obtained was ground. Melting point: 80-85 ℃.

Example 2

VESTANAT T1890 (trimer of IPDI) -sorbitol adduct

Sorbitol, DBTL, Jonol CP were dissolved in acetone (50% concentration). Then, IPDI-T1890 was dissolved in acetone to a concentration of 50% and added dropwise to the sorbitol solution at 40 ℃ over 2 hours, followed by stirring for 16 hours, with NCO content =0.1 wt%. The acetone was removed in a vacuum oven at 40 ℃. The solid obtained is ground.

Diels-Alder reaction

Materials:

isophorone bis (sorbitan carbamate) (IPDI-SA) (Evonik Industries AG),

1, 4-bis (bromomethyl) benzene (97%, Aldrich),

sodium hydride (60% dispersion in mineral oil, Aldrich),

tetrahydrofuran (THF, anhydrous, greater than or equal to 99.9%, ABCR),

diethyl phosphate (>99.0%, Fluka),

carbon disulfide (anhydrous, not less than 99.9%, Aldrich),

zinc 2-ethylhexanoate (97%, Aldrich) and

acetonitrile (anhydrous, 99.8%, Fluka),

used as supplied.

Zinc chloride (Aldrich) was dried under vacuum and stored under a protective gas atmosphere.

All other solvents were used without further purification.

And (3) characterization:

hydrogen nuclei were subjected to the following reaction using a Bruker AM250 spectrometer operating at 500MHz¹H nuclear spin resonance (NMR) spectroscopic analysis. All samples were dissolved in CDCl₃Or DMSO-d₆In (1). The scale was calibrated to the internal standard trimethylsilane (TMS, =0.00 ppm).

On Polymer Laboratories (Varian) PL-GPC 50Plus integration System, using THF as eluent at 35 ℃ and 1mL min^-1The flow rate of (A) was measured by Gel Permeation Chromatography (GPC), the integrated system comprising an autosampler, a 5 μm bead size PL-Gel front column (50 × 7.5.5 mm), a 5 μm hybrid PL-Gel E-column (300 × 7.5.5 mm), three 5 μm hybrid PL-Gel C columns (300 × 7.5.5 mm), and a differential refractive index detector with a flow rate from 160 to 6 × 10⁶g mol^-1Linear poly (styrene) standards ofArticle and from 700 to 2 × 10⁶g mol^-1The SEC system was calibrated with a linear poly (methyl methacrylate) standard. Molecular weight relative to PS was reported in the present study.

Mass spectrometry was performed on an IXQ mass spectrometer (ThermoFisher Scientific) fitted with an atmospheric pressure ionization source operating in nebulizer-assisted electrospray mode, which was used in positive ion mode. The instrument was calibrated in the 195-1822m/z range using a standard sample containing a mixture of caffeine, Met-Arg-Phe-Ala acetate (MRFA), and fluorinated phosphazene (Ultramark 1621) (Aldrich). Sample (c =0.1-0.2mg mL)^-1) Dissolved in a 3:2v/v mixture of THF and methanol and mixed with sodium acetate (0.014 mg mL)^-1) And (4) doping. All spectra were obtained with a spray voltage of 5kV and a capillary temperature of 275 ℃ in the m/z range of 150-. Nitrogen was used as the protective gas (flow: not more than 45%) and helium was used as the auxiliary gas (flow: not more than 5%). Theoretical mass calculations were performed using IsotopeViewer software version 1.0.

Synthesis of 1, 4-phenylenebis (methylene) bis ((diethoxyphosphoryl) methanedithioformate) (P-bis-linker) (1)

P-di-linker 1 was synthesized by the following procedure. In a two-necked flask equipped with a reflux condenser and a magnetic stirrer, a solution of diethyl phosphite (5.3 mL, 41.2 mmol) in anhydrous THF (20 mL) was added dropwise under nitrogen to a suspension of NaH (1.64 g, 41.2 mmol) in THF (40 mL). Once the evolution of hydrogen was complete, the mixture was heated at reflux for 10 minutes. After cooling to room temperature, the mixture was further cooled in a liquid nitrogen bath. Then CS was added dropwise₂(12.26 mL, 203.6 mmol) and the mixture was allowed to warm to room temperature. Stirring was continued for an additional 30 minutes, after which 1, 4-bis (bromomethylbenzene) (5.44 g) dissolved in anhydrous THF (40 mL) was added dropwise to the reaction mixture. Stirring was continued at room temperature for 3 hours, then 200mL of hexane was added and the reaction mixture was filtered. The violet filtrate was collected and the solvent removed under reduced pressure. The crude product was purified by column chromatography on silica gel using initially hexane as eluent to remove impurities and then ethyl acetate as eluent to collect product 1. After removal of the solvent under reduced pressure, P-bis-linker 1 was obtained as a solid (60% yield) with a dark purplish red color.¹H NMR(250MHz,DMSO-d₆,25℃)：(ppm)=7.36(s,4H,ArH),4.57(s,4H,-CH₂S-),4.21-4.08(m,8H,-OCH₂CH₃),1.30-1.21(t,J=7Hz,12H,-CH₂CH₃) ESI-MS + Na (m/z) calculated: 553.01, respectively; the found value is: 553.12.

scheme 1. Synthesis of Dithio phosphate Dilinker 1

Diels-alder reaction: staged polymerization of P-di-linker 1 and IPDI-SA2, which resulted in product 3.

A typical polymerization procedure is as follows: both IPDI-SA and P-di-linker were dissolved separately in acetonitrile and mixed in a 1:1 ratio (based on functional groups) so that the concentration of the resulting solution was 1.8M. To the reaction mixture was added 1.1 equivalents of zinc chloride (ZnCl)₂). This mixture was heated to 50 ℃ for 4 hours. The viscous mixture was diluted in 1mL chloroform and extracted with water to remove ZnCl₂And dried (85-96% yield). This staged polymerization reaction was carried out in the presence of acetonitrile to obtain the product 3. The product was analyzed by SEC. After 2 hours, M_n=8100g mol^-1。

Scheme 2. cycloaddition product 3 (a simplified structure of one possible regio/stereoisomer is shown), which is formed by the HDA reaction of 1 and 2.

3 retro diels-alder reaction (rDA): a typical reaction procedure is as follows: 100mg of Polymer 3 was dissolved in 5mL of acetonitrile. The solution was heated in a pressure tube with stirring for 40 minutes to 140 ℃. The temperature was varied from 120 to 160 ℃ and the reaction time was varied from 10 to 160 minutes. The reaction mixture was then rapidly chilled with liquid nitrogen. A sample of the rDA product (0.1 mL) was diluted in THF (0.4 mL) and analyzed by GPC and mass spectrometry.

The results are shown in FIG. 1.

Claims (27)

1. The reaction product of:

A) at least one isocyanate and/or amine of the formula 1 having at least two functional groups per molecule

It has the following definitions:

n＝0、1,

X＝NCO、NH₂、NHA,

a ═ H, simultaneously or independently of one another, is an alkyl radical having from 1 to 16 carbon atoms, a cyclic hydrocarbon radical, an aromatic hydrocarbon radical, which optionally contains heteroatoms and/or functional groups,

r is an aliphatic or cycloaliphatic hydrocarbon radical, which optionally contains heteroatoms and/or functional groups, and

B) at least one diene of formula 2 having functional groups

It has the following definitions:

Y＝CH₂OH、COOH、COOA、CH₂NH₂、CH₂NHA，

A. z and R¹-R⁴Simultaneously or independently of one another, is an alkyl radical having 1 to 16 carbon atoms, a cyclic hydrocarbon radical, an aromatic hydrocarbon radical, which optionally contains heteroatoms and/or functional groups,

wherein all functional groups X of A) have been reacted with an equivalent amount of B).

2. The reaction product according to claim 1, wherein at the group A, R, Z or R¹-R⁴The functional groups mentioned in the definition of (1) are double bonds.

3. The reaction product according to claim 1, wherein aliphatic and cycloaliphatic diisocyanates are used as component A), alone or in mixtures.

4. The reaction product according to claim 3, wherein the aliphatic and cycloaliphatic diisocyanates are IPDI, TMDI, HDI and/or H₁₂MDI。

5. The reaction product according to any of claims 1 to 4, wherein isocyanurates are used, alone or in a mixture.

6. The reaction product according to claim 5, wherein the isocyanurate is IPDI, HDI and/or H₁₂Trimers of MDI.

7. The reaction product according to claim 1, wherein a diamine selected from the group consisting of: 1, 3-and 1, 4-diaminomethylcyclohexane, hexane-1, 6-diamine, 2,2, 4-and/or 2,4, 4-trimethylhexane-1, 6-amine and mixtures of the aforementioned, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine, 4,4 '-methylenedicyclohexyldiamine, 2, 4-methylenedicyclohexyldiamine, 2,2' -methylenedicyclohexyldiamine and also any mixtures of 4,4 '-methylenedicyclohexyldiamine, 2, 4-methylenedicyclohexyldiamine and 2,2' -methylenedicyclohexyldiamine, polyetherdiamines.

8. The reaction product according to any of claims 1 to 4, wherein sorbitol and/or sorbic acid is used as component B).

9. The reaction product according to any of claims 1 to 4, wherein component B) used is a retinoid of the following general formula 5:

vitamin A and derivatives

F＝OH、COOH、COOK、CHO,

Wherein K is an alkyl group containing 1 to 6 carbon atoms, a cyclic hydrocarbon group, an aromatic hydrocarbon group, which group optionally contains heteroatoms and/or functional groups.

10. The reaction product according to claim 9, wherein the functional groups mentioned in the definition of the group K are double bonds.

11. The reaction product according to any of claims 1 to 4, wherein component B) used is a retinoid of formula 6:

vitamin A.

12. Use of the reaction product of:

A) at least one isocyanate and/or amine of the formula 1 having at least two functional groups per molecule

It has the following definitions:

n＝0、1,

X＝NCO、NH₂、NHA,

a ═ H, simultaneously or independently of one another, is an alkyl radical having from 1 to 16 carbon atoms, a cyclic hydrocarbon radical, an aromatic hydrocarbon radical, which optionally contains heteroatoms and/or functional groups,

r is an aliphatic or cycloaliphatic hydrocarbon radical, which optionally contains heteroatoms and/or functional groups, and

B) at least one diene of formula 2 having functional groups

It has the following definitions:

Y＝CH₂OH、COOH、COOA、CH₂NH₂、CH₂NHA，

A. z and R¹-R⁴Simultaneously or independently of one another, is an alkyl radical having 1 to 16 carbon atoms, a cyclic hydrocarbon radical, an aromatic hydrocarbon radical, which optionally contains heteroatoms and/or functional groups,

wherein all functional groups X of A) have been reacted with an equivalent amount of B).

13. Use of the reaction product according to claim 12, wherein at the group A, R, Z or R¹-R⁴The functional groups mentioned in the definition of (1) are double bonds.

14. Use of the reaction product according to claim 12, wherein a bifunctional polymer prepared by Atom Transfer Radical Polymerization (ATRP) is used as dienophile component.

15. Use of a reaction product according to claim 12, wherein a compound containing a carbon-sulfur double bond is used as dienophile component.

16. Use of a reaction product according to claim 12, wherein a dithioester is used as dienophile component.

17. Use of a reaction product according to claim 12, wherein a compound having the following structure is used as dienophile component

Wherein Z is an electron withdrawing group, R^mIs a polyvalent organic group, and n is a number of 2 to 20.

18. Use of a reaction product according to claim 17, wherein n is a number from 2 to 4.

19. Use of a reaction product according to claim 17, wherein R^mAre polyvalent organic radicals, polyfunctional alcohols based on branched or linear alkyl groups, aromatic or combinations of alkyl and aromatic groups, polyfunctional halogenated compounds, polyfunctional carboxylic acids or polyfunctional amines, or polymers.

20. Use of the reaction product according to any of claims 17 to 19, wherein Z is 2-pyridyl, phosphoryl, sulfonyl, cyano or trifluoromethyl.

21. Use of the reaction product according to any of claims 12 to 19 in adhesives, moulding compounds, inks, sealants, coatings, varnishes, paints or composites.

22. Use of the reaction product according to any of claims 12 to 19 for the preparation of a moulded article.

23. Use of the reaction product according to claim 22 for the preparation of a moulded article via a rapid prototyping process.

24. Use of the reaction product according to any of claims 12 to 19, wherein sorbitol and/or sorbic acid is used as component B).

25. Use of a reaction product according to any of claims 12 to 19, wherein component B) used is a retinoid of the following general formula 5:

vitamin A and derivatives

F＝OH、COOH、COOK、CHO,

Wherein K is an alkyl group containing 1 to 6 carbon atoms, a cyclic hydrocarbon group, an aromatic hydrocarbon group, which group optionally contains heteroatoms and/or functional groups.

26. Use of a reaction product according to claim 25, wherein the functional groups mentioned in the definition of group K are double bonds.

27. Use of a reaction product according to any of claims 12 to 19, wherein component B) used is a retinoid compound of formula 6:

vitamin A.